* * * * *

DESCRIPTION The present invention relates to new polymers and presensitized positive and negative offset printing plates.

More particularly, it relates tc polymers suitable to form, when mixed to diazonium salts and photoinitiators, a photosensitive composition suitable to produce presensitized positive and negative offset printing plates having improved properties.

It is known that the properties required to a polymer for the production of presensitized positive and negative offset printing plates are:

- good compatibility with diazonium salts; - good stability of the photosensitive mixture (i.e. polymer plus diazonium salt);

- good adhesion of the photosensitive mixture to the support;

- high difference of solubility in aqueous developing solutions between light exposed and non-exposed areas; - high development speed; i.e., when eposed for the same time to a lamp having an emission spectrum comprised within 200 to 500 n , the complete elimination of the non-exposed photosensitive mixture should be as quick as possible;

- high ink retention of the mixture hardened upon exposition to a lamp having an emission spectrum comprised within 200 and

500 nm;

- high retention degree of the ink by the hardened mixture;

- high mechanical resistance of the hardened mixture.

It is also known that up to now several polymers have been prepared in order to find a polymer having all the above

mentioned properties at the highiest possible degree. Examples of said polymers are disclosed in the following documents : US-4,289,838, US- ,316,949, UK-1,358,922, UK-1,463,818, UK-1, 74,073, UK-A-2,057,704 and EP-A-182,642. However, none of the known polymers is characterized by the optimization of the above mentioned properties. More particularly, polymers having a high development speed tend to have poor mechanical resistance, and vice versa. On the other hand, these two properties are known to the artisan to be critical for an economical industrial use of presensitized positive and negative offset printing plates.

It has now been found that the above properties may be optimized by means of a compound of the formula

(I) wherein R is an aliphatic chain having from 2 to 6 carbon atoms and 1 or 2 double bonds;

R' is a covalent bond, a cycloalkyl group having from 5 to 6 carbon atoms, a saturated aliphatic chain having from 2 to 10 carbon atoms and 2 or 4 oxygen atoms which are part of -CO-0- groups, a saturated aliphatic chain having from 2 to 10 carbon atoms and

1 or 2 oxygen atoms of ether groups, a saturated heterocyclic ring having from 3 to 4 carbon atoms and 2 oxygen atoms, a group of the formula

where Z is SO , a saturated straight ^• or branched alkyl chain having from 1 to 3 carbon atoms or an alkylphenyl group where the alkyl moiety is saturated, straight or branched and has 1 to 3 carbon atoms; R" is a group of the formula

wherein Z* is a covalent bond, 0, S, CH , CO, NH,

SO , SO NH, CH =CH , N=N, NHC0NH, NHCSNH or CH -C-CH,

3 3, and

R-, R' , R,,and R' , the same or different, are H, CH , OCH , OC H , Cl, SO H or CH ₂ -0-CH ;

Y and Y', the same or different, are hydrogen or, together with X and X', respectively, complete a cycloaliphatic ring having from 5 to 6 carbon atoms; and

X and X', the same or different, are a covalent bond when Y and Y ¹ respectively, are hydrogen or, together with Y and Y', respectively, complete a cycloaliphatic ring having from 5 to 6 carbon atoms; and n is an integer from 2 to 60.

Preferably, the polymer according to the present invention has a weight average molecular weight value of from 1,200 to 33,000, an amine number (mg HCl/g polymer) of from 1 to 27, and an unsaturation equivalent (milliequivalents of Br /g) of from 400 to 560.

Preferred meanings of R are:

-CH=CH-CH=CH-, -CH -CH-=CH-CH -, CH =C-CH -, -CH=CH- and -CH=C(CH )- Preferably R ¹ is a covalent bond (ERL-4206 Union Carbide), -C00CH (ERL-4221 Union Carbide) ", -—Q< >-— (ERL-4234 Union

Carbide), (ERL-4299 Un. Carb. ⁾ , or

-Q— /> Z is CH -C-CH S0 ₂ , CH , or

CH -C-C H . 3 ι 6 5

In comparison with the polymers of the state of the art, the compounds of formula (I) have the advantage of producing presensitized positive and negative offset printing plates having both high development speed and high mechanical resistance. Moreover, they are also endowed with high adhesivity to the substrate and this implies the advantage of requiring a lower graining of the support and a lower thickness of the photosensitive layer.

A second object of this invention is to provide a process for preparing a polymer of the formula I. Said process essentially consists of preparing an unsaturated polyhydroxypolyester having an epoxy end group and condensing said epoxy end group with an amino group of a suitable aromatic diamine according to the following scheme:

0 0

/\ / \

(n+1) H00C-R-C00H + (n+1) CH-CH-X-R'-X'-CH-CH

Y'

(AC) (EP)

Y OH OH Y' Y OH 0 i I /\

HOOC-R-COO+CH-CH-X-R'-X*-C IH-CIH-OCO-R-OCO--CIH-CIH-X-R'-X'-CH-CH

I n Y'

(II)

(DM) where n,R,Y,X,R',Z',R ,R' ,R ,R* , have the meanings mentioned above in relation to the formula (I).

Preferred meanigs of (AC) are the following unsaturat ^' ed ^" aliphatic dicarboxylic acids : maleic, fu aric, muconic, hydromuconic, itaconic, citraconic and mesaconic.

Preferred meanings of (EP) are the followig diepoxides: vinyl cyclohexene dioxide (ERL-4206 Union Carbide), 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane-carboxylate (ERL-4221 Union Carbide),

2-(3,4-epoxycyclohexyl-5,5-spiro-3,4— epoxy)-cyclohexane-metadioxane (ERL-4234 Union Carbide), bis(3,4-epoxycyclohexyl)-adipate (ERL-4299 Un.Carb.), and diglycidyl ethers of bisphenol A, S, ACP, and F.

The first reaction step, which relates to the preparation of the unsaturated polyhydroxy polyester (II), is preferably

carried out by reacting substantially equimolar amounts of (AC) and (EP) in the presence of a suitable accelerating agent at a temperature of from 10 to 150°C, optionally in the presence of one or more suitable inert solvents, until the acidity number of the intermediate product (II) reaches the theoretical value calculated for the desired molecular weight.

Examples of suitable accelerating agents are AMC1 and AMC2 by Aerojet Strategic Propulsion (chromium salt soluble in organic solvents), p-toluensulphonic acid, triphenylphosphine, and trimeth Iammonium bromide.

Examples of suitable organic solvents are butyl acetate, methyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, and ethyl acetate.

The second reaction step comprises the addition of the aromatic diamine (DM) to the intermediate product (II). Said step is preferably performed by adding to the reaction mixture resulting from the first step an amount of (DM) substantially sufficient to react with the epoxy end groups of intermediate (II) at a temperature of from 50 to 150°C. The running of the reaction is monitored by means of known analytical techniques (spectrophotometry FTIR and/or primary amine number).

At the end of the reaction it is preferred not to remove the solvents and to stabilize the polymer (I) toward oxidation by adding small amounts of known antioxidant agents such as, for example, hydroquinone, 2,6-di-terbutyl-p.cresole, butyr- aldoxime, 1,5-naphthalenediol, di-hydroxyazobenzene, 2- mercaptobenzothiazole, and the like.

A further object of this invention is to provide a presensitized positive or negative offset printing plate formed

by a layer sensitive to the light having wavelength of from 200 to 500 nm spread on a suitable support, said photosensitive layer comprising essentially a polymer, a photosensitive diazocompound, a dye and a compound selected from photoinitiators, sensitizers, and diazides, characterized in that the polymer is a compound of the formula ⁽ I).

The support is preferably a metal sheet, e.g. aluminium, suitably treated according to known techniques such as degreasing, pickling, graining, buffing, electrochemical anodization, surface protection treatments and the like. Examples of said treatments are disclosed by the patents US-2,882,153, US-2,882,154, US-2,946,683, US-3,160,506, US-3,330,743, US-3,440,050, US-3,891,516, US-3,963,594, US-4,072,589, UK-1,235,863, UK-1,544,315, DE-907,147, DE-1,160,733.

In general, the diazocompounds present in photosensitive compositions according to the present invention are consisting of positive or negative light-sensitive diazocompounds commonly used for lithographic printing plates. Preferably, these compounds are aromatic diazocompounds wich have been condensed with products containing reactive carbonyl groups such as formaldehyde and paraformaldehyde. Said diazocompounds may be reacted with copulating agents such as, e.g., aromatic acid compounds such as benzenesulphonate, toluenesulphonate, unsubstituted or substituted sulphonated benzophenones. Examples of these diazocompounds are disclosed by the following patents: US-2,922,715, US-2,946,683, US-3,300,309, US- 3,591,575, US-3,113,865, US-3,661,573, US-3,050,502, US-3,311,605, US-3,163,633, UK-1,277,428, EP-A-74,580 and EP-135,616.

In turn, examples of photoinitiators, photosensitizers and diazides are disclosed by the patents UK-1,482,953,

US-3,954,475, US-4,059,400, US-4,058,401, US-3,775,113,

US-3,887,450, US-3,895,949, US-4,043,819, US-3,046,120, US-3,046,121 and US-3,211,553.

The addition of a dye has substantially the aim of enabling to visualize the non-exposed portions with respect to those exposed to a lamp having an emission spectrum coprised within 200 and 500 nm. Usually, it is preferably used any known dye that is compatible with the other components of the photosensitive layer and is easily removable by the developing bath from the non-exposed portions.

Several kinds of developing products, also called "developers", have been tested in the development tests performed on the printing plates of this invention. The developers having the following percent composition (w/w) are cited among those which proved to better remove, after exposure to the actinic light, the non printing portions: alkylsulphonate (or alkylbenzenesulphonate) 5.0 13.0 ethylene glycol monophenylether 3.0 8.0 sodium etasilicate pentahydrate 0.6 1.2 deion zed water _2_L__ _ZZ_._.

100.0 100.0

Dodecyl-, decyl-, nonyl-, and octylbenzenesulphonate, dodecyl-, decyl-, nonyl-, and octylsulphonate of organic and inorganic bases, and the mixture thereof are examples of suitable alkyl- and alkylbenzene-sulphonates. Typical examples of suitable organic and inorganic bases are: triethanolamine, sodium, potassium and lithium. A specific example of a suitable developing composition

TM comprises: 1,000 g of Sulfetal TL 40 by Zschimmer & Schwarz,

600 g of phenyl glycol by BASF, 100 of sodium metasilicate pentahydrate by A.C.E.F. (Italy), and 2,300 of deionized water.

The following examples illustrates the invention without, however, limiting it in any way.

I__A__J___IS_l__2g Po^y_mers_of_the_Inventi_on 210.2 g of muconic acid (1.0 moles), 366.2 g of bis-(3,4-epoxycyclohexyl)-adipate (1.0 moles) and 290.4 g of butyl acetate (2.5 moles) were placed in a 2-litres reactor equipped with stirrer, electric heating jacket, thermometer, electric thermostat and double jacket condensing coil.

The mixture was stirred at room temperature for 5 minutes and then brought to 80°C. Upon reaching 80°C, 6.68 g of AMC-2 (0.04 moles), catalyst consisting of an organic chromium salt manufactured by Aerojet Strategic Propulsion Co. U.S.A, diluted in 58.1 g of butyl acetate (0.5 moles), were added in about 30 minutes. The temperature was then raised to 100°C and maintained until the acid number of the product was of 20 mg KOH/g. 91.3 g of methylcellosolve (1.2 moles) were then added and the temperature was reduced very qickly to 50°C. The acid number of the thus obtained product was of 18 mg KOH/g and the weight average molecular weight value of 16,000. 19.4 g of 4,4*-diaminodiphenylmethane (0.01 moles) ^" were added and the temperature was raised to 80°C and maintained until 50% reduction of the primary amine absorption band ^" (FTIR spectrophotometer) . At the end of the reaction, 2.20 g of hydroquinone (0.02 moles) were added in order to stabilize the product toward oxidation. All polymers (P) listed in table I were prepared in a similar way, using the same solvents, the same catalyst and the same molar ratios (1.0 moles of unsaturated dicarboxylic acid, 1.0 moles of diepoxide, 0.1 moles of diamine); the codes listed in table I identify the following starting materials: yQI§_y£§I§_l_.__i__j_£boxy _>i li _i C_aci.ds_^AC).

AC-0 muconic acid AC-1 hydromuconic acid AC-2 itaconic acid

_.i-_B2_.i_._-§-.i.I£2

EP-0 bis-(3,4 epoxycyclohexyDadipate (ERL-4299 Union Carbide)

EP-1 bisphenol A diglycidyl ether EP-2 bisphenol S diglycidyl ether EP-3 bisphenol ACP diglycidyl ether EP-4 bisphenol F diglycidyl ether EP-5 3,4-epoxycyclohexylmethyl-3,4-epoxycylohexane— carboxylate (ERL-4221 Union Carbide)

EP-6 vinylcyclohexene dioxide (ERL-4206 Union Carbide) EP-7 2-(3,4-epoxycyclohex l-5,5-sp ro-3,4-epoxycyclohexane— metadioxane (ERL-4234 Union Carbide)

__i§!_i_!§_._.._._!_!_.

DM-0 4,4'-diamine-diphenylmethane

DM-1 4,4'-diamine-diphenyIsuIphone

DM-2 benzidine

DM-4 2,2' -di chloro-5,5 ^, -dimethoxybenzidi ne

DM-6 5-amino-2-(p-aminoan line)-benzenesulphonic acid

DM-7 5-amino-2-(4-amino-m-toluidine)-benzenesulphonic acid

DM-8 4,4'-isopropylidenediani line

DM-10 4,4'-diaminodiphenylamine

DM-12 6,6'-thiodimetani lie acid

DM-13 4,4'-diamino-carbani lide

DM-15 C.I. Disperse Black 2 (C.I. 11255)

DM-16 Bistramine Brown G (C.I. 11275)

DM-17 Cellitazol BGL (C.I. 11245)

TABLE I

EXAMPLE_21 Corneari_son_Products In the tests described below, the polymers prepared according to examples No. 1-20 were also compared with the following commercial products:

PA : C.A.P. (cellulose acetophthalate), Eastman Kodak

(R) PB : Macrynal SM 510 N/21 modified with maleic anhydride in molar ratio 1:0.12. Macrynal SM 510 N/21 is an acrylic

pol-ycondensate (60% in methyl acetate) by Hoechst.

(R) PC : Movital B 60 T modified with maleic anhydride in molar ratio 1:0.12. Movital B 60 T is a terpolymer from vinyl butyral/vinyl acetate/vinyl alcohol (71/2/27 parts by weight) by Hoechst.

(R) PD : Formvar 12/85T modified with maleic anhydride in molar ratio 1:0.12. Formvar 12/85T is a condensate from polyvinyl alcohol/formaldehyde by Monsanto.

I_____ _. P- _. §___22-74 Ehgtosensjti e_Comgositi.on_and_Print Qg_PJLate

The photosensitive composition of this invention mainly comprises the following ingredients:

Parts (w/w) (P) polymer of the formula (I) according to this invention 68.5-74.0

(DZ) diazo compound 20.0-12.0

(CO) dye 2.5- 3.0

(F0) photoinitiator or (SE) sensitizer or (ZD) diazide 6.5- 8.0

(LI) levelling agent 2.3- 3.0 dissolved in 1,500-1,700 parts of a diluent mixture or in a non-aqueous and non-reactive diluent.

The expression "non-reactive diluents" is intended to mean all those diluents which cannot undergo reaction under the action of light beams having a wavelenght of from 180 to 550 nanometers or heat to form polymers or condensates.

The codes listed in table II identify the following ingredients: E°i_!___J__._..__!_.

- polymers (P1-P20) of examples 1-20

- comparison products (PA, PB, PC, and PD)

- polymer (P21) disclosed in example No. 1 i§-.-_Di-.ϊ-._--_i-.§_--_---2 having the following general formula:

are identified as follows:

DZ-0 : A =A =A =A = H, A = -CH -, B = NH, n = 1-6

J = p-toluenesulphonate DZ-1 . A =A =A =A = H, A = -CH -, B = NH, n = 1-6

J = 2-hydroxy-4-methoxy-benzophenonesulphonate DZ-2 : A =A =A = H, A = 0CH , A = 4,4'-oxymethanediphenylether

B = NH, n = 1-6, J = p-toluenesulphonate DZ-3 : A = -N(CH ) , A = H, A =A = 0CH ,

A = 4,4*-oxymethanediphenylether, B = NH, n = 1-6,

J = 2-hydroxy-4-methoxy-benzophenone-5-sulphonate DZ-4 : A = OH, A =A =A = H, A = 4,4'-oxymethanediphenylether

B = -CH=CH-, n = 1-6, J = p-toluenesulphonate DZ-5 : A =A =A = H, A = 0CH , A = 4,4'-oxymethanediphenylether

B = -NH-C0-, n = 1-6,

J = 2-hydroxy-4-methoxybenzophenone-5-sulphonate DZ-6 : A = N(CH ) , A =A =A = H, A = benzene-1,4-oxymethane

B = -SO -, n = 1-6, J = p-toluenesulphonate

DZ-7 A = N (CH ) A = H, A =A = 0CH_, 1 _. _! -. 5 4 _>

A = 4,4 ' -oxymethanedi pheny lether, B = -0-, n = 1 -6,

J = 2-hydroxy-4-methoxybenzophenone-5-su lphonate

DZ-8 A^A ₂ = H, A ₃ =A ₄ = 0CH ₃ , A ₄ = CH.,,

A =dimethoxy-4,4'-oxymethanediphenylether, B = -S-, n = 1-6, J = p-toluenesulphonate

DZ-9 A =A = H, A =A = OC H , A = 4,4'-oxymethanediphenyl- ether, B = -NH-C0-, n = 1-6, J = p-toluenesulphonate

DZ-10 A = CH , A = H, A =A = OC H , A = 4,4'-oxymethanedi- phenylether, B = -S-, n = 1-6, J = p-toluenesulphonate

DZ-11 A = CH , A = H, A =A = OCH , A = 4,4'-oxymethanedi- phenylether, B = -S-, n = 1-6, J = p-toluenesulphonate

_-_._.___--_._.

CO-0 Victoria Blue FB (BASF) C0-1 Victoria Blue FBO (BASF) C0-2 Duasyne (Hoechst) CO-3 Etasol BF Rosa Bengala (Colori Baglie) CO-4 Crystal Violet (BASF) C0-5 Methyl Violet (BASF) CO-6 Sudan Blue (BASF)

E!_2_-2iGi£i__-.2-.______._-_.

TM

FO-0 Quantacure PDO (Ward Blankinsop S Co.) F0-1 Quantacure B1 F0-2 Quantacure B3

T „. FO-3 Quantacure B4

TM _ FO-4 Quantacure B5

TM F0-5 Quantacure CTX

TM FO-6 Quantacure MTX

TM FO-7 Quantacure ITX

TM F0-8 Quantacure DBS

TM

FO-9 : Quantacure EPD

TM

F0-10 : Quantacure EOB

F0-11 : Quantacure BEA

TM

F0-10 : Quantacure EOB

TM

F0-12 Quantacure DMB

TM

FO-13 Darocur 1173 (Merck) A.G.

TM

FO-14 Darocur 1116

FO-15 : Darocur ^' 1664

1TM

FO-16 Irgacure 651 (Ciba-Geigy ⁾

____Q§i__i___-I.5_.-i_il2

SE-0 Acridine Orange SE-1 Acridine Yellow SE-2 Phosphine SE-3 Benzoflavine SE-4 Setoflavine SE-5 Michler's Ketone SE-6 4-(methoxy)-benzylamino-2,5-diethoxybenzene diazo zinc chloride

SE-7 p-N,N-dibutylaminobenzene diazo zinc chloride

SE-8 4-pyrrolidine-3-methylbenzene diazo tetrafluoborate

SE-9 CH -C H,-NH-C H -N„ ⁺ .BF, 3 64 64 2 4

SE-10 4-pyrrolidine-3-methoxybenzene diazo tetrafluoborate

SE-11 CH -C H,-NH- H -N„ ⁺ .Cl 1/2 ZnCl„ 3 6 4 6 4 2 2

SE-12 4-(p-tolylmercapto)-2,5-diethoxybenzene diazo zinc chloride SE-13: 4-(p-tolylmercapto)-2,5-diethoxybenzene diazo tetrafluo- borate SE-14: 4-(p-tolylmercapto)-2,5-dimethoxybenzene diazo zinc chloride SE-15: 4-morpholino-2,5-dibutoxybenzene diazo zinc chloride

SE-16: 4-morpholino-2,5-dibutoxybenzene diazo tetrafluoborate

SE-17: morpholino-2,5-diethoxybenzene diazo zinc chloride

SE-18: morpholino-2,5-diethoxybenzene diazo tetrafluoborate

D azi_des_ _a ZD ZD-0 : 4,4*-diazidodiphenylmethane

ZD-1 : diphenyldiazide

ZD-2 : dimethoxydiphenyldiazide

ZD-3 : p-aminodiphenyldiazide

ZD-4 : stilbenediazide ZD-5 : azidosti Ibene benzoazide

ZD-6 : diazido disti Ibenephenone

ZD-7 : 2,6-bis-(4'-azidobenzylidene)-cyclohexanone

L§_.§iiiQ9_§9§Q-_§____._--_

LI-0 : Fluorad™ FC 430 (3M)

TM LI-1 : Fluorad FC 431 (3M)

__£§BS£S__i2D_2f_._i!}_._.-!!_2£2§§Q§i_;i_!_l_._;2 _!22§iϊi2!3_.§D_l_.EriD_.iD9

Plate

In a 2-liters glass vessel equipped with a stirrer having variable speed (60-2,500 r.p.m.) and a cooling jacket, 1,500 parts by weight of methylcellosolve and 18 parts by weight of a polydiazodiphenylamine paraformaldehyde condensate salified with p.toluensulphonic acid (DZ-0) were placed while stirring at 150 r.p.m., when the solution was clear 70 parts by weight of a dry polymer product of formula P1, prepared as disclosed in example No. 1, were added.

When the solution became again clear under stirring at 150

TM r.p.m., 6.5 parts by weight of Quantacure PD0 (FO-0) were added; once obtained a clear solution, 3.0 parts of Victoria

Blue FB (CO-0) were added under stirring and keeping the temperature below 30°C, 2.5 parts by weight of levelling agent

TM Fluorad FC 430 (LI-0) were then added with stirring. The thus obtained product was uniformly coated by means of an automatic

2 device, in the amount of 14.2 g/m , on an aluminium support of

2 2 m having a thickness of 0.3 mm which had previously undergone the following treatments:

- alkaline cleaning and subsequent washing

- pickling with inorganic acids

- surface graining by electrochemical treatment and subsequent washing - cleaning by an acid bath and subsequent washing

- anodizing by immersion in an acid bath under direct current

- surface treatment (0.2 g/m ) with sodium silicate of the formula Na SiO 0_ and subsequent washing

- additional protective treatment by an aqueous solution of

2 polyvinylphosphonic acid (0.2 g/m ) and subsequent washing.

The thus obtained photosensitive printing plate was dried in an infrared oven, with forced ventilation, for 3 minutes at a temperature of 70°C. After cooling, the plate was stored in a dark place where the humidity degree was 60%, protected from air by means of a sealed polyethylene sheet.

After drying the final weight of the photosensitive coating

2 composition was of 0.9 g/m .

By a similar way and using the same solvents, the photosensitive plates (L) listed in table II (plates 1-52) were prepared. The concentration of the ingredients used was as follows:

70 parts by weight of a polymer (P) according to Table I or comparison example No. 21 (P21) or of a comparison product

(PA, PB, PC, PD), and 18 parts by weight of diazonium salts (DZ) for plates No. 1-24

and plate No.52, or 12 parts by weight of diazonium salts (DZ) for plates No.

25-52, and 6.5 parts by weight of sensitizer ⁽ SE), or photoinitiator (FO), or diazides (ZD),

3 parts by weight of dye (CO), and

TM 2 parts by weight of the levelling agent Fluorad FC 430

(LI-0).

42 L 21 P17/DZ-1/F0-13/C0-0 43 L 22 P18/DZ-2/F0-14/C0-1 44 L 23 P19/DZ-3/F0-15/C0-2 45 L 24 P20/DZ-4/FO-16/CO-3 46 L 25 P1/DZ-11/SE-0/C0-0 47 L 26 P2/DZ-0/SE-0/C0-0 48 L 27 P2/DZ-1/SE-1/C0-1 49 L 28 P3/DZ-2/SE-2/C0-2 50 L 29 P4/DZ-3/SE-3/C0-3 51 L 30 P5/DZ-4/SE-4/C0-4 52 L 31 P6/DZ-5/SE-5/C0-5 53 L 32 P7/DZ-6/SE-6/C0-6 54 L 33 P8/DZ-7/SE-7/C0-0 55 L 34 P9/DZ-8/SE-8/C0-1 56 L 35 P10/DZ-9/SE-9/C0-2 57 L 36 P11/DZ-10/SE-10/C0-3 58 L 37 P12/DZ-11/SE-11/C0-4 59 L 38 P13/DZ-0/SE-12/C0-5 60 L 39 P14/DZ-1/SE-13/C0-6 61 L 40 P15/DZ-2/SE-14/CO-0 62 L 41 P16/DZ-3/SE-15/C0-1 63 L 42 P17/DZ-4/SE-16/C0-2 64 L 43 P18/DZ-5/SE-17/C0-3 65 L 44 P19/DZ-6/SE-18/C0-4 66 L 45 P20/DZ-7/ZD-0/CO-0 67 L 46 P1/DZ-8/ZD-1/C0-1 68 L 47 P2/DZ-9/ZD-2/C0-2 69 L 48 P3/DZ-10/ZD-3/C0-3 70 L 49 P4/DZ-11/ZD-4/C0-4 71 L 50 P5/DZ-0/ZD-5/CO-5

72 L 51 F6/DZ-1 /ZD-6/C0-6 iXAMPLES_74-125

I_.§iy§ti2D_-2_!_._[ _._P_!2-_2§§D_ii-Li_.--__!EiD--iQ9_Ei§____§ The photosensitive printing plates L1-L52, prepared as described in Examples 22-74 above, were exposed, developed and evaluated for a number of properties enabling to assess their performances in conditions of actual use.

Plates L1-L52 were exposed keeping constant the following parameters:

- printing plate dimension (77 x 103 cm)

- kind of exposer (Mod. 87 by Lastra Attrezzature)

- exposition time (25 seconds)

- vacuum applied to plate + film during exposition (93%) - power of the actinic light lamp (2000 Watt)

- emission spectrum of the actinic lamp (360 nanometers)

- distance of the lamp from the exposed surface (70 cm)

- film showing a figure that is superimposed upon the plate.

After exposure, plates L1-L52 were developed keeping constant the following parameters:

- automatic developer with a bath at 2C°C (SM 140 by Lastra Attrezzature)

- developer (aqueous-alkaline at pH = 10.0)

Developed printing plates were evaluated for the following properties:

A ⁼ _.e elθEΪn9_rate cm/min) at a temperature of 20°C.

Data were evaluated on a scale ranging from 1 to 6, where 1 is the worst and 6 the best value.

^{B =} £j.§3Q_.iQ_.____2l_£!ie_Q2_-_2£i___.i_!9_22£-_i2Q§ The dimensions (in microns) of the remaining particles of

layer not removed by the developing solution and their quantity (number per square centimeter) were evaluated by means of a stereo microscope at 40 magnifications.

On all plates L1-L52 no residual particle was detected, therefore this characteristic was deemed excellent for all the plates and is not shown in Table III that summarizes the pistes evaluation. ^{c =} iQJ_iQ9___ _. __9E-.__ ^{on a} "Stouffer" scale ⁽ 21 steps ⁾ when the printing plate inked by a rubber roller retains an amount of ink of 3 microns on its surface. The values are evaluated on a scale ranging from 1 to 21, where 1 is the worst and 21 the best value.

D ⁼ £J__-§QiiQ§_i§_2i_-__l_--.Q2Q-B£iQ-iQ9-.B2£-_i2Q-._-.f _.__£_iQ__iQ9

The ink should not stain at all the non-printing portions of the plate. The values are evaluated on a scale ranging from 0 to 10, where 0 is the worst and 10 the best value. All the plates L1-L52 had value 10, therefore this characteristic was deemed excellent for all the plates and is not shown in Table III. E = iQk_£etent|on_bγ__the_2r|nting_2late

A plate uniformly inked with an amount of litographic ink corresponding to 3 micron of thickness, should not deink when immersed for 5 minutes in an aqueous solution of organic and inorganic compounds containing surfactants and having a pH of 4.5 at 20-23°C (Dynafount R 21 by

P.CO.Holland). Deinking is evaluated on a Stouffer Scale 1-21. The ^' number of steps inked before and after the immersion should be the same. The values are evaluated on a scale ranging from 1 to 21 where 1 is the worst and 21 the best value.

<~ ⁼ §_!£asion_resistance_before_i _> QkiQg

At 25°C, a 23 x 10 cm plate portion, previously weighed on a precision balance, is placed on the surface of an electromechanical abrasimeter. The abrasion was performed with a metal plug weighing 1700 grams provided with a standard abrasive removable surface which was renewed for each sample. The plate surface was submitted to abrasion for 60 cycles at the rate of 1 cycle per second; the plate was weighed after the treatment and the percent weigh loss was calculated.

The percent abrasion is given as percent weigh loss and the better it is, the lower is the measured value.

^{G =} Bi§_.S_y§§E_ϊ!_iJ__._B£iQ__iQ9

A test was carried out on a sample of photosensitive plate on which several Stouffer scales were impressed (at the edges - in the center and at the middle portions of the plate). To this purpose the plate was mounted on a printing machine for continuos modules, with standard ink, standard fountain solution, standard paper. Printing was performed at the rate of 20,000 copies per hour, for 5 hours, and both the wear of the inked Stouffer scales after printing and the scale image on printed paper were evaluated. Each non-inked and/or non-printed scale step corresponds to a printing wear of 5%. The lower is the plate wear while printing, the lower is the percent measured value. Complete evaluation of plates L1-L52, for the above mentionedproperties, is shown in the following

IABLE_III

ExanjBJ.e Pj.ate A C E F G

No. No. devel inking inking abrasion printing oping degree reten resis wear rate tion ance

74 L 1 5 10 10 16 18

75 L 2 4 8 8 22 20

76 L 3 4 11 11 8 5

77 L 4 5 10 10 10 4 78 L 5 3 12 12 5 2

79 L 6 4 11 11 8 5

80 L 7 3 12 12 5 2

81 L 8 4 10 10 8 7

82 L 9 4 10 10 8 6 83 L 10 4 6 6 10 10

84 L 11 6 3 3 30 40

85 L 12 6 3 3 40 50

86 L 13 6 2 2 30 40

87 L 14 6 4 4 25 35 88 L 15 4 10 10 8 5

89 L 16 4 10 10 5 3

90 L 17 4 10 10 5 5

91 L 18 4 10 10 6 6

92 L 19 5 10 10 5 8 93 L 20 5 10 10 12 16

94 L 21 4 8 8 20 22

95 L 22 4 11 11 8 5

96 L 23 5 10 10 10 7

97 L 24 3 12 12 5 3 98 L 25 4 12 12 5 5